1. Field of the Invention
The present invention relates to a semiconductor device using a metal silicate film as a gate insulating film, to a method for manufacturing such a semiconductor device, to an apparatus for forming such a film in a semiconductor device, and to a method for forming such a high-dielectric-constant film in a semiconductor device.
2. Background Art
Accompanying the miniaturization of semiconductor devices, the reduction of thickness of gate insulating films has been demanded. The reduction of thickness of silicon oxide films and silicon oxynitride films (hereafter referred to as “silicon oxide film and the like”), which are used as conventional gate insulating films, is limited due to increase in leak current, and it is difficult to reduce the SiO2-converted film thickness to 1.5 nm or less. Therefore, there has been proposed a method for inhibiting leak current by using a high-dielectric-constant film, such as a metal oxide film, a metal silicate film and a metal aluminate film, which has a higher specific inductive capacity higher than that of silicon oxide film and the like as the gate insulating film; and by increasing the physical film thickness of the gate insulating film.
However, when the high-dielectric-constant film is used as the gate insulating film, and a polysilicon electrode is used as the gate electrode, there has been a problem that impurities doped in the polysilicon electrode diffuse into the substrate through the gate insulating film when the impurities are activated, and the transistor properties are deteriorated.
In order to solve this problem, a method for introducing nitrogen into the high-dielectric-constant film has been proposed.
Specifically, there has been proposed method for forming a high-dielectric constant film composed of a zirconium oxynitride layer or a hafnium oxynitride layer, by forming a metal layer composed of zirconium or hafnium on a substrate, and oxynitriding the metal layer (refer to e.g., Japanese Patent Laid-Open No. 2000-58832).
Furthermore, there has also been proposed a method for laminating a lower barrier film consisting of a hafnium-containing silicon oxynitride film, a high-dielectric-constant film consisting of a silicon-containing hafnium oxide film, and an upper barrier film consisting of a silicon-containing hafnium oxide film that contains nitrogen to form a gate insulating film and for controlling the composition of a metal (M), oxygen (O), nitrogen (N) and silicon (Si) in the high-dielectric-constant film and the lower barrier film (refer to e.g., Japanese Patent Laid-Open No. 2003-8011).
In a thin-film formation using a high-dielectric-constant material, the ALD (atomic layer deposition) method is generally used. In this method, material gasses are alternately supplied while resetting the chamber to the original state to form each atomic layer.
For example, the formation of a hafnium oxide (HfO2) film as a high-dielectric-constant film will be specifically described. First, the chamber is evacuated, argon gas is flowed in the chamber, and the pressure in the chamber is maintained to 0.2 Torr. In this state, hafnium tetramethylethylamide [Hf(N(CH3)(C2H5)2)4] is flowed into the chamber while controlling the flow rate, and the Hf material is vaporized and adsorbed on the surface of the substrate. Then, the chamber is purged, and an oxidizing gas such as ozone gas is introduced. Thereafter, the chamber is purged. By repeating such steps for several tens of times, a hafnium oxide (HfO2) film of a thickness of several nanometers can be formed on the surface of the substrate.
The introduction of nitrogen into a high-dielectric-constant film reduces flat-band-voltage shift (hereafter referred to as “Vfb shift”) due to the diffusion of impurities. This is estimated because the high-dielectric-constant gate insulating film is densified by nitriding treatment, and the diffusion of impurities is restricted.
However, in the above-described conventional method, initial Vfb shift due to the effect of fixed charge or the like is large, and there has been a problem that satisfactory transistor characteristics cannot obtained particularly in P-channel MIS transistors.
In addition, a high-dielectric-constant thin film formed using the ALD method generally contains several percent impurities. This is considered because carbon (C), hydrogen (H) or chlorine (Cl) included in material gas using the ALD method remains and is incorporated in the formed film. The impurities remaining in the high-dielectric-constant film may cause fixed charge and trap, and the characteristics of the film is damaged.